Spectrally sensitized photographic silver halide emulsions

ABSTRACT

WHEREIN M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amino group.   wherein Z represents a member selected from the group consisting of CH and N; R3 and R4 each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an arylthio group, an aryl group, an amino group, an alkylamino group, an arylamino group and an aralkylamino group; and A represents a member selected from the group consisting of:   wherein Y and Y1 each represents a nonmetallic atomic group necessary for forming a heterocyclic ring; R and R1 each represents a member selected from the group consisting of an alkyl group, a substituted alkyl group, an aryl group, an allyl group and an aralkyl group; R2 represents a member selected from the group consisting of a halogen atom and an alkyl group; X represents an anion, n stands for 1 or 2; and m stands for 1 or 2, and a compound shown by general formula (II)   A photographic silver halide emulsion composition comprising a sensitizing dye shown by general formula (I)

Milo oi; all,

[54] SIPIECWALLW SIENMTHZIEIW PHOTOORAPHHC siwmi HALWE IEMFULEHUNS [72]Inventors: Alitiro Soto; lllliroslhi Misti; lifieisulte Shilm;

Mastmno Minute, all of Kanagawa, Japan [73] Assignee: Fuji Photo FilmCo, Ltd., Kanagawa,

Japan [22] Filed: Dec. 4, 11967 [21] Appl. No.: 687,469

[30] Foreign Application Priority Date Dec. 3, 1966 Japan ..41/79255[52] Ufi. Cll ..96/126, 96/133 [51] Int. Cl. .JGmc 11/28, G03c 1/20 [58]Field oil Search ..96/l04, 126

[56] References Cited UNITED STATES PATENTS 2,933,390 4/1960 McFall eta1. ..96/104 X FOREIGN PATENTS OR APPLICATIONS 168,596 11/1965 U.S.S.R...96/104 OTHER PUBLICATIONS I-Iamer, The Cyanine Dyes and RelatedCompounds, (1964), p. 207.

Primary Examiner-William D. Martin Assistant Examiner-David CohenAtwrneySughrue, Rothwell, Mion, Zinn & Macpeak 57 AnsrnAcr Aphotographic silver halide emulsion composition comprising a sensitizingdye shown by general formula (I) alkyl group; X represents an anion, nstands for 1 or 2; and m stands for l or 2, and a compound shown bygeneral formula R3-Z( INHA-NH-I TZR3 V Y 14 R4 (ll) S 03M S 03M S 03M@CONH S aM wherein M represents a member selected from the groupconsisting of a hydrogen atom, an alkali metal, ammonium. and an aminogroup.

6 Claims, No Drawings SPECTRALLY SENSllTlZlED PHOTOG RAH-11M: SILVERHALHIDE EMULSEONS BACKGROUND OF THE INVENTION 1. Field of the InventionThe present invention relates generally to spectrally sensitizedphotographic silver halide emulsions and more particularly tosupersensitized photographic silver halide emulsions.

2. Description of the Prior Art It is well known that by incorporating asensitizing dye in a silver halide emulsion in the case of producing aphotographic silver halide emulsion, the wavelength region oflight-sensitivity ofthe llilVCfl' halide emulsion its enlarged and thesilver halide emuluitm in Mpectrally sensitized. Alan, it is known thatthe menaitivity of u silver halide emulsion sensitized by a definitesensitizing dye may be varied according to the type of emulsion intowhich the sensitizing dye is introduced. Furthermore, the sensitivity ofa definite emulsion sensitized by a definite sen sitizing dye can bevaried by changing the properties of the emulsion. For instance, thesensitivity of a silver halide emulsion can be increased by increasingthe silver ion concentration or by reducing the hydrogen ionconcentration or by a combination thereof. However, the silver halideemulsion sensitized in such a way has the disadvantage that thepreservability thereof is generally bad.

There is, however, a so-called supersensitizing action, that is, aphenomenon of increasing the sensitivity of a silver halide emulsion byincorporating in the emulsion a compound along with a sensitizing dyewithout changing the properties of the emulsion as mentioned above,e.g., without changing the silver ion concentration and the hydrogen ionconcentration of the emulsion. The compound which is used together withthe sen sitizing dye is generally called a supersensitizer.

As the spectral sensitizer for a photographic silver halide emulsion,there are usually used dicarbocyanines. Among them, a mesosubstituteddicarbocyanine has a merit in that the formation of fog in a silverhalide emulsion sensitized by it is very low as compared with the caseof using mesounsubstituted dicarbocyanines. In some cases, however, theaddition of the mesosubstituted dicarbocyanine to a silver halideemulsion is accompanied by a reduction in sensitivity. Particularly inthe case of using a dicarbocyanine, the mesoposition of which has beensubstituted with a halogen, the sensitivity of the silver halideemulsion containing the dicarbocyanine is reduced markedly.

However, if it is possible to increase the sensitivity of a silverhalide emulsion by incorporating therein the aforesaid spectralsensitizer together with a certain supersensitizer, a photographicsilver halide emulsion having high sensitivity and low fog can beobtained, and this is very desirable and useful for practical purposes.

Thus, an object of the present invention is to provide a photographicsilver halide emulsion in which a mesosub stituted carbocyanine and aspecific supersensitizer, as mentioned below, have been incorporated toimprove the sensitivity thereof and reduce the formation of fogs.Another object of the present invention is to provide a photographiclight-sensitive element having high sensitivity and low fog.

SUMMARY OF THE INVENTION These and other objects of this invention canbe achieved by incorporating in a photographic silver halide emulsionthe mesosubstituted carbocyanine shown by the following general formula(I) together with the compound shown by the following general formula(II):

wherein Y and Y, each represents a nonmetallicatomic group necessary forforming a heterocyclic ring. such as, a thiazole, a benzothiazole, anuphthothiazole, naphthoselenazole, a selenazole, a benzoselenazole, abenzoxazole, a naphthoxazole, an oxazole, a Z-quinoline, a 4-quinoline,an indolenine and the like; R and R, each represents an alkyl group,such as, an ethyl group, a propyl group, and the like; a substitutedalkyl group, such as, a 2-hydroxyethyl group, a Z-methoxyethyl group, acarboxymethyl group, a Zcarboxyethyl group, a 3- carboxypropyl group, a4-carboxybutyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a4-sulfobutyl group, a carbomethoxymethoxy group, a carboethoxymethylgroup, a carbomethoxyethyl group, a carhoethoxyethyl group, and thelike; an urylgroup. an ullyl group; or an aralkyl group; R, represents ahalogen atom such as a fluorine atom, a chlorine atom, a bromine atomand the like; or an alkyl group such as a methyl group, an ethyl group,a'propyl group and the like; X represents an anion; n is l or 2; and mis l (in the case of forming an intramolecular salt) or2; and

wherein Z represents CH or N; R and R, each represents a halogen atom, ahydroxyl group, an alkoxyl group, an aryloxyl group, an arylthio group,an aryl group, an amino group, an alkylamino group, an arylamino group,or an aralkylamino group; and A represents a group selected from thefollowing:

I 5 our s 03H DETAILED DESCRlPTlON OF THE lNVENTlON Typical examples ofthe mesosubstituted dicarbocyanines used in the present invention areshown below together with methods of preparing them.

PREPARATION 1 Preparation of mesoethyl-3, 3-diethylthiadicarbocyanineiodide;

in a mixture of ml. of acetic anhydride and 1 ml. of acetic acid therewere dissolved 1.5 g. of 2-methyl-3-ethylbenzothiazolium iodide and 0.6g. of l-ethyl-2-anilinoacrolein anil, and they were reacted by heatingthe system for 2 minutes under refluxing. After cooling, the crystalthus precipitated was recovered by filtration. The crystal was washedwith water and recrystallized from ethanol to provide 0.5 g. of dye(I-l) having a melting point of 240 C. (d). The absorption maximum ofthe dye in methanol was 648 my" By the same methods as above, themesosubstituted carbocyanines shown by formulas (I-2), (l-3 (I-4) and(L5) can be prepared.

In a mixture of 20 ml. of pyridine and 5 ml. of acetic acid weredissolved 2.5 g. of 3-carboXymethyl-5,6-dimethylbenzothiazolium bromideand l g. of l-ethyl-2-anilinoacrolein anil. The solution was heated for3 minutes under refluxing and 4 ml. of triethanolamine was added to thesolution. Thereafter, they were reacted by heating the system for 2minutes under refluxing. After cooling, water was added to the productand the crystal precipitated was recovered by filtration andrecrystallized from methanol to provide 0.3 g. of dye (l-6) having amelting point of 194 C. (d) and an absorption maximum in methanol of 663mu.

The same procedure as in the case of preparing dye (H) was repeatedusing, however, l-chloro-2-anilinoacrolein anil instead ofl-ethyl-2-anilinoacrolein anil to provide dye (l-7) having a meltingpoint of 252 C. (d), and an absorption maximum in methanol of 646 my Thesame procedure as in the case of preparing dye (H) was repeated usingl-bromo-2-anilinoacrolein anil instead of l-ethyl-2-anilinoacrolein anilto provide dye (l-8) having a melting point of 221 C. (d), and anabsorption maximum in methanol of 646 my.

SOaNa OzNa OaNa S OaNa OaNa S OaNa OZNE CHaCH- OsNa Among the compoundsshown by general formula (11), the compounds in which Z is 1I t l 1atis,the compounds hav' ing an S-triazine nucleus may be prepared by knownmethods. Also, among the compounds in which Z is -CH=, that is, thecompounds having a pyrimidine nucleus, those compounds wherein R and Rare halogen atoms or various amino groups, or the compounds wherein R orR is bonded to the pyrimidine nucleus by an ether bond or a thioetherbond may be prepared by procedures of the type shown in the followingexamples. 7

PREPARATION 5 Preparation of the compound shown by the formula (11-25)as shown above:

Mixed with m1. of acetone were 1 1.0 g. of 2,4,6- trichloropyrimidineand 12.4 g. of sodium 4,4'-diaminostilbene-2,2'-disulfonate and themixture was stirred at 55-65 C. Hydrochloric acid formed during reactionwas neutralized by the addition of a 10 percent aqueous sodium carbonatesolution whereby the reaction mixture was maintained at the state offrom neutral to weak acid. After the reaction was finished, the reactionmixture was ice-cooled to form a crystal of compound (II-25 which wasrecovered by filtration.

PREPARATION 6 Preparation of the compound shown by formula (ll-23 Amixture of 14.1 g. of sodium 4,4-

bis(dichloropyrimidinylamino)-stilbene-2,2'-disulfonate, 4.4 g. ofthiophenol, and 1.6 g. of sodium hydroxide was heated under refluxing ina solvent mixture of 70 ml. of water and 20 ml. of dioxane for about 2.5hours. After cooling, the precipitate thus formed was removed byfiltration and from the filtrate was removed dimethylformamide bydistillation under a reduced pressure. The residue thus obtained wasdissolved in a solvent mixture of water and acetone and about 5 ml. ofconcentrated hydrochloric acid was added and the crystal thus formed wasrecovered by filtration. The crystal of compound (II-23) was washed withwater and dried.

PREPARATION 7 Preparation of the compound shown by formula (11-24):

A mixture of 14.1 g. of sodium4,4'-bis-(dichloropyrimidinyl)-stilbene-2,2-disulfonate, 4.4 g. ofthiophenol and 1.6 g. of sodium hydroxide was heated under refluxing ina solvent mixture of 70 m1. of water and 20 ml. of dioxane. After theend of water, about 5 ml. of concentrated hydrochloric acid was added tothe reaction mixture to precipitate the product, which was recovered byfiltration under suction and washed with water and methanol followed bydrying.

The addition amount of the mesosubstituted carbocyanine sensitizing dyeused in the present invention is suitably from about 0.002 to 0.2 g. perone gram molecule of silver halide contained in the silver halideemulsion and the addition amount of the super-sensitizer having generalformula (11) is suitably from about 0.05 to 10 g. per one gram of silverhalide in the silver halide emulsion. Furthermore, the suitable ratio ofsensitizing dye (l) to compound (11) is from about 1:2 to 1:200.

Sensitizing dye (1) may be added to a silver halide emulsion by anymethod well known in this field. Compound (11) may be added to a silverhalide emulsion as a solution of the compound in an organic solvent,such as methanol or ethanol. Sensitizing dye (l) and compound (11) areadded to a silver halide emulsion prior to coating. Sensitizing dye (1)may be added to a silver halide emulsion before or after the addition ofcom pound (11) or may be added together with the latter.

1n the silver halide emulsion of this invention, various silver saltsmay be used such as silver chloride, silver bromide, silver iodide,silver iodobromide, silver chlorobromide, silver chloroiodobromide andthe like. Moreover, to the silver halide emulsion there may be added theusual additives such as a chemical sensitizer, a hardening agent, anantifoggant, a wetting agent, a stabilizer, a plasticizer, a developmentaccelerator, and an antibronzing agent. Also, the silver halide emulsionof this invention may contain a coupler capable of forming dye by colordevelopment such as a cyan coupler without affecting the merits of theaddition of the compounds of this invention. I V

The photographic silver halide emulsion may be applied to a suitablesupport, such as a glass plate, a film of a cellulose derivative, asynthetic resin film, a baryta-coated paper and the like.

The invention will further be explained by the following example.

EXAMPLE A silver chlorobromide gelatin emulsion containing 40 molpercent bromine and having incorporated therein the mesosubstitutedcarbocyanine sensitizing dye (l) was applied to a triacetyl cellulosefilm base. Also, a silver chlorobromide emulsion having the same silverhalide concentration as above and having incorporated therein thesensitizing dye (I) and compound (ll) was applied to a triacetylcellulose film base. After drying, the photographic light-sensitivefilms were redexposed to a light source of 2,666 K. in color temperaturethrough Fuji No. 7 Filter (transmitting light having longer wave lengthsthan 590 my.) and then developed for 6 minutes at C. in the developerhaving the following composition.

N-Methyl-p-Aminiphenol Sulfate 2.0 g. Hydroquinone 4.0 g. Sodium Sulfite40 g. Sodium Carbonate (Monohydrate) 28 g. Potassium Bromide l g. Waterto make 1,000 ml.

While assuming that the red sensitivity of the silver halide emulsioncontaining only sensitizing dye (l) is 100, the red sensitivities of thesilver halide emulsions of this invention containing variouscombinations of sensitizing dye (l) and compound (II) were compared, Theresults are shown in the following table. 1

sensitizing dye (I) Compound (11) Red (mm/gram mol of (mg/gram mol ofsensi- Ag halide) Ag halide) tivity Fog [-8 (12) 100 0. 04 l-H (12; .ll-ili $300) 135 0. 04 l-X (l2 ll-ll 301)) 229 0. 04 l-i (u) 100 0. 04l-l g1!) ll-lH (300) [74 0. 04 l-[ il) I H1 (300) 27!) (l. ()4 l 4 (10).100 0.04 1 10) ll-IH E300) lili 0. 04 l-4 10) ll-(l 300) 809 (l. 04 l-311) 100 0. 05 F3 11) ll-llt (300) 118 0. 04 I-3 11) ll-(l (300) 224 0.04 I5 l1) 100 0. 04 '1-5 (11; 11-18 (300) 151 0. 04 I-& (11 11-45 (300)288 0. 04 I-9 (9) 100 0. 04 1-9 (9) 6 (300) 537 0. 04 I-9 (9) 11-4 (300)380 0. 04 I-9 (9) II-1 (300) 331 0. 04 I-9 (9) 11-7 (300) 389 0. 04 1-7(9) 11-8 (300) 389 0. 04 1-7 (9) 11-5 (300) 214 0. 04 1-7 (9) 11-2 (300)389 0. 04 I-7 9) 11-10 (300) 372 0. 04 I-7 (9) 11-11 (300) 347 0. 04 I-7(9) 11-12 (300) 275 0. 04 I-7 9) 11-13 (300) 372 0. 04 I-7 (9) 11-14(300) 288 0. 04 I-7 E9) 11-15 (300) 601 0. 04 I-7 9) II16 300) 316 0. 041-7 (9) 11-17 (300) 275 0. 04 I-7 59) 11-20 (300) 178 0. 04 I-7 9) 1I-21(300) 191 0. 04 I-6 (9) 100 0. 05 Hi (9) I16 (300) 130 0. 04 [-2 E13)100 0. 06 1-2 13) 11-6 (300) 316 0. 04 I-2 213) 11-22 (300) 204 0. 04I-S 12) 100 0. 04 I-8 (12) 11-23 (300) 204 0. 04 I-7 (9) 100 0. 04 I-7135 0. 04

What is claimed is:

1. A photographic silver halide emulsion composition comprising a silverhalide and a sensitizing dye shown by the following formula wherein Zrepresents a member selected from the group consisting of CH and N; Rand R each represents a member selected from the group consisting of ahalogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, anarylthio group, an aryl group, an amino group, an alkylamino group, anarylamino group and an aralkylamino group; and A represents amemberselected from the group consisting of:

s do? wherein M represents a member selected from the group consistingof a hydrogen atom, an alkali metal, ammonium, and an amino group.

2. The photographic silver halide emulsion, according to claim 1 whereinsaid sensitizing dye is incorporated in the silver halide emulsion in anamount of from about 0.002 to 0.2 g. per one gram molecule of the silverhalide in said emulsion.

3. The photographic silver halide emulsion according to claim 1 whereinsaid compound is incorporated in said silver halide emulsion in anamount of from about 0.05 to 10 g. per one gram molecule of the silverhalide in the emulsion.

is X- /n-l Iii wherein Y and Y each represents a nonmetallic atomicgroup necessary for forming a heterocyclic ring; R and R, eachrepresents a member selected-from the group consisting of an alkylgroup, a substituted alkyl group, an aryl group, an allyl group and anaralkyl group; R represents an alkyl group; X represents an anion, nstands for l or 2; and m stands for l or 2, and from about 0.05 to gramsper 1 gram molecule of said silver halide of a compound shown by theformula wherein Z represents a member selected from the group consistingof CH and N; R and R each represents a member selected from the groupconsisting of a halogen atom, a hydroxyl group, an alkoxyl group, anarylorty group, an

arylthio group, an aryl group, an amino group an alkylamino group, anarylamino group and an aralkylamino group; and A represents a memberselected from the group consisting of:

S 0 M S 0 M S 0 M -QQ' S 03M S 03M S 03M wherein M represents a memberselected from the group consisting of a hydrogen atom, an alkali metal,ammonium, and an amino group, wherein the weight ratio of saidsensitizing dye .to said compound varies from I :2 to 1:200.

' l i V V w I w a m a:

2. The photographic silver halide emulsion, according to claim 1 whereinsaid sensitizing dye is incorporated in the silver halide emulsion in anamount of from about 0.002 to 0.2 g. per one gram molecule of the silverhalide in said emulsion.
 3. The photographic silver halide emulsionaccording to claim 1 wherein said compound is incorporated in saidsilver halide emulsion in an amount of from about 0.05 to 10 g. per onegram molecule of the silver halide in the emulsion.
 4. The photographicsilver halide emulsion according to claim 1 wherein the weight ratio ofsaid sensitizing dye to said compound to be incorporated in said silverhalide emulsion is from about 1:2 to 1:200.
 5. A photographiclight-sensitive element comprising a support bearing thereon at leastone layer containing the photographic silver halide emulsion of claim 1.6. A photographic silver halide emulsion composition comprising a silverhalide and from 0.002 to 0.2 g. per 1 gram molecule of said silverhalide of a sensitizing dye shown by the formula